Abstract

The synthesis of a number of yttrium metallocenes based on the phenanthrene-fused Cp ligand PCpR (R = H, Me, Ph) is reported. Acid−base (σ-bond metathesis) reactions between the parent HPCpR ligands and Y(CH2SiMe3)3(THF)2 afford the monomeric alkyl complexes Y(PCpR)2(CH2SiMe3)(THF) (R = H, 1; Me, 2; Ph, 3). Salt metathesis between Li+PCpMe− and YCl3 in THF similarly affords the monomeric chloride complex Y(PCpMe)2(Cl)(THF) (4), which reacts further with methyllithium to generate the bridging “ate” complex Y(PCpMe)2(μ-Me)2Li(THF)2 (5). Complex 3 undergoes rapid hydrogenolysis in the presence of phenylsilane to afford the crystalline bridging hydride dimer [Y(PCpPh)2]2(μ-H)2 (6). The X-ray structures of complexes 2 and 6 are reported along with the solution behaviour of 2.

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